JP6109428B2 - Lubricant composition - Google Patents

Description

FIELD OF THE DISCLOSURE The present disclosure relates generally to amines as ashless fuel additives, as well as lubricant compositions containing amines.

Description of Related Art Many internal combustion engines, such as those found in ships, trains, motorcycles, scooters, ATVs, and lawn equipment, burn a mixture of fuel and lubricant compositions. Specifically, the mixture is introduced into a cylinder of an engine (engine) and burned to move the piston and the engine. Lubricant compositions are added to fuels to lubricate various engine components (eg, cylinders and pistons) and to optimize combustion, fuel consumption, emissions and engine life. The lubricant composition includes a base oil and additives, such as antiwear additives, dispersants, and detergents.

  However, during combustion, impurities in the fuel and additives, such as overbased detergents and other additives including metals, do not burn completely and do not “burn out”. As a result, ash is formed. Some of the formed ash remains in the cylinder, causing accumulation of “sediment” and even “plate out” on engine components (eg cylinders and pistons) Damage the engine, reduce fuel consumption, and ultimately reduce engine life.

  For example, marine vessels are supported by the combustion of a mixture of crude fuels that often contain high concentrations of sulfur and lubricant compositions during the voyage. The lubricant composition used in this mixture includes an overbased detergent such as calcium carbonate. Overbased detergents are present to neutralize the acid formed by sulfur combustion. However, in emission-restricted (EC) areas (eg, coastal areas with high environmental standards), these ocean-going ships are instead typically used to reduce pollutants generated during combustion. Supported by combustion of a more refined fuel mixture containing less sulfur and a lubricant composition. When further refined, less sulfur fuel is burned and less acid is formed. Next, there is an excess of overbased detergent that forms ash, plate out on the cylinder wall and other engine parts, thereby damaging the engine, reducing fuel consumption and ultimately reducing engine life Let For this reason, there is a need for a lubricant composition that can accommodate changes in fuel sulfur concentration (eg, between crude and refined fuel). Such a lubricant composition should reduce ash formation, thereby minimizing engine damage, improving fuel economy, and controlling emissions regardless of changes in fuel sulfur concentration.

SUMMARY OF THE DISCLOSURE A lubricant composition for a compression ignition internal combustion engine is disclosed. The lubricant composition comprises (i) an amine as an ashless fuel additive having a total base number (TBN) of about 200 to about 600 mg KOH / g when tested according to ASTM D2896; and (ii) a metal sulfonate A detergent selected from salts, phenolic metal salts (metal phenolates), salicylic acid metal salts, carboxylic acid metal salts, thiophosphonic acid metal salts, and combinations thereof. The lubricant composition has a TBN of about 20 to about 130 mg KOH / g when tested according to ASTM D2896. The amine contributes more than about 30% of the TBN of the lubricating oil composition.

  A method of lubricating an internal combustion engine with a lubricant composition is also disclosed. A method for lubricating an internal combustion engine includes a step of injecting fuel and a lubricant composition into a cylinder to form a mixture, and a step of burning the mixture by compression ignition.

DETAILED DESCRIPTION OF THE DISCLOSURE A lubricant composition for a compression ignition internal combustion engine (“lubricant composition”) is disclosed herein. The lubricant composition includes an amine as an ashless fuel additive (“amine”) and a detergent. The lubricant composition may comprise one or more amines, i.e. one amine or two or more amines. The amine is basic, soluble in base oils and fuels, chemically stable, and does not produce ash upon combustion (ie, as understood by ASTM D 874 and in the art). Ashless). Usually, the term “ashless” means the absence of significant amounts of metals such as sodium, potassium, calcium and the like.

  The amine neutralizes the acid but, as mentioned above, does not form ash that damages engine components, reduces fuel consumption, and ultimately reduces engine life. The amine effectively neutralizes the acid because of its basicity. A minimal amount of amine can be added to neutralize or “treat” the fuel. That is, amines can be used at low “treatment rates”. The basicity of an amine is quantified by its total base number (“TBN”). The TBN can be calculated theoretically and can be determined by ASTM D2896 and / or ASTM D4739. The amine, when tested according to ASTM D2896, is greater than about 150 mg KOH / g, alternatively greater than about 195 mg KOH / g, alternatively greater than about 200 mg KOH / g, alternatively greater than about 250 mg KOH / g, alternatively greater than about 270 mg KOH / g. / G, or more than about 290 mg KOH / g, alternatively more than about 310 mg KOH / g, alternatively about 200 mg KOH / g to about 800 mg KOH / g, alternatively about 200 mg KOH / g to about 600 mg KOH / g, or About 275 mg KOH / g to about 600 mg KOH / g, alternatively about 250 mg KOH / g to about 600 mg KOH / g, alternatively about 250 mg KOH / g to about 550 mg KOH / g, alternatively about 500 mg KOH / g to about 60 mg KOH / g or may have a TBN of about 500 mg KOH / g to about 800mg KOH / g,. Alternatively, the amine is at least about 200 mg KOH / g, at least about 250 mg KOH / g, at least about 300 mg KOH / g, at least about 350 mg KOH / g, at least about 450 mg KOH / g, or at least when tested according to ASTM D2896. It may have a TBN of about 500 mg KOH / g.

  The lubricant composition also has TBN. Various components of the lubricant composition, such as amines, detergents, dispersants, etc. contribute to the TBN of the lubricant composition. In various embodiments, the lubricant composition is about 20 mg KOH / g to about 130 mg KOH / g, alternatively about 20 mg KOH / g to about 90 mg KOH / g, alternatively about 30 mg KOH / g, when tested according to ASTM D2896. g to about 90 mg KOH / g, alternatively about 35 mg KOH / g to about 85 mg KOH / g, alternatively about 40 mg KOH / g to about 110 mg KOH / g, alternatively about 50 mg KOH / g to about 90 mg KOH / g, alternatively about 60 mg It has a TBN of KOH / g to about 80 mg KOH / g. In some embodiments, the amine contributes to the TBN of the lubricant composition by greater than about 30%, alternatively greater than about 40%, alternatively greater than 50%. For example, if the amine contributes more than 40% to the TBN of the lubricant composition having a TBN of 70 mg KOH / g, the amine contributes more than 28 mg KOH / g to the TBN of the lubricant composition. The greater the amine contributes to the TBN of the lubricant composition, the less ash-producing detergent is needed to maintain the desired TBN of the lubricant. That is, the greater the effect of amine on the TBN of the lubricant composition, the less need for a detergent that produces ash in the lubricant composition. Thus, the amine contributes to the TBN of the lubricating oil composition and allows the use of less detergent in the lubricant composition. In a preferred embodiment, the amine TBN contribution to the lubricating oil composition TBN is greater than the detergent TBN contribution to the lubricating oil composition TBN.

  In addition, a method of treating the lubricant composition with an amine is also disclosed herein. The method includes adding an amine to the lubricant composition. In this method, the amine addition step typically involves adding the lubricant composition and the amine to less than 45 wt%, alternatively less than 40 wt%, alternatively 35 wt%, based on the total weight of the lubricant composition. Less than, alternatively less than 30% by weight, alternatively less than 25% by weight, alternatively less than 20% by weight, alternatively less than 15% by weight, alternatively less than 10% by weight, alternatively less than 5% by weight, alternatively from 1% to 45% by weight, alternatively from 5% to 40% by weight. , Or 8 to 40% by mass, or 15 to 40% by mass of amine in terms of the treatment ratio. Of course, the treatment rate is directly related to the TBN number of the amine. Typically, the higher the amine TBN, the lower the treat rate. Of course, the treatment rate is lower in the case of a lubricant composition comprising a detergent, for example in the case of partial replacement of the detergent with an amine.

The amine can contain one or more amine groups. The amine can include a tertiary amine group, a secondary amine group, a primary amine group, or a combination thereof. In various embodiments, the amine has a weight average molecular weight (M _{w) of} about 100 to about 700 g / mol, alternatively about 100 to about 550 g / mol, alternatively about 100 to about 400 g / mol, alternatively about 100 to about 250 g / mol. ).

In various embodiments, the amine has the general formula:
C _W H _X N _Y O _Z
(Wherein, W is 5-30, X is 20-60, Y is 1-5, and Z is 0-5)
Have

（式中、Ｒ^１、Ｒ^２、及びＲ^３は独立して水素原子又はＣ_１〜Ｃ_１５炭化水素基である）
を有する。一実施態様では、Ｒ^１、Ｒ^２、及びＲ^３のうち少なくとも１つは分枝鎖状又は環状の炭化水素基である。理論により拘束されるものではないが、様々な実施態様では、アミンに結合される１つ以上の分枝鎖状又は環状の炭化水素基の存在は、アミンの潤滑剤組成物への溶解性を容易にするものと考えられる。即ち、Ｒ^１、Ｒ^２、及びＲ^３のうち少なくとも１つが分枝鎖状又は環状の炭化水素基である場合、様々な温度（例えば、−４℃、４℃、４５℃、又は６０℃）で様々な時間（例えば、９０日）にわたって保存される時に、潤滑剤組成物は均一なままであり、アミンは潤滑剤組成物中に沈殿しない（アミン及び潤滑剤組成物の他の成分は優れた溶解性を有する）。 In various preferred embodiments, the amine has the following general structure:

(Wherein R ¹ , R ² , and R ³ are independently a hydrogen atom or a C ₁ -C ₁₅ hydrocarbon group)
Have In one embodiment, at least one of R ¹ , R ² , and R ³ is a branched or cyclic hydrocarbon group. While not being bound by theory, in various embodiments, the presence of one or more branched or cyclic hydrocarbon groups attached to the amine may increase the solubility of the amine in the lubricant composition. It is thought to facilitate. That is, when at least one of R ¹ , R ² , and R ³ is a branched or cyclic hydrocarbon group, various temperatures (eg, −4 ° C., 4 ° C., 45 ° C., or 60 ° C.) The lubricant composition remains homogeneous and the amine does not precipitate in the lubricant composition when stored for various times (eg, 90 days) (the amine and other components of the lubricant composition are excellent) Have high solubility).

（式中、Ｒ^４は直鎖状又は環状のＣ_３〜Ｃ_１１炭化水素基である）
を有する。ここで上記の構造（Ｉ）を参照すると、構造（ＩＩ）の実施態様では、Ｒ^１及びＲ^２は水素原子であり、且つＲ^３は分枝鎖状又は環状の炭化水素基である。構造（ＩＩ）の１つ以上の特別な実施態様では、Ｒ^４は直鎖状のＣ_９〜Ｃ_１１炭化水素基である。ここで上記の構造（Ｉ）を参照すると、この構造（ＩＩ）の更に特別な実施態様では、Ｒ^１及びＲ^２は水素原子であり、且つＲ^３は分枝鎖状の炭化水素基（Ｒ^４を含む）である。 In one such embodiment, the amine has the following general structure:

(Wherein R ⁴ is a linear or cyclic C _{3 to} C ₁₁ hydrocarbon group)
Have Referring now to structure (I) above, in the embodiment of structure (II), R ¹ and R ² are hydrogen atoms and R ³ is a branched or cyclic hydrocarbon group. In one or more special embodiments of structure (II), R ⁴ is a linear C ₉ -C ₁₁ hydrocarbon group. Referring now to structure (I) above, in a more particular embodiment of this structure (II), R ¹ and R ² are hydrogen atoms and R ³ is a branched hydrocarbon group (R ⁴ ).

In another such embodiment, at least two of R ¹ , R ² , and R ³ of structure (I) are branched or cyclic hydrocarbon groups. In such embodiments, the amine is a secondary or tertiary amine.

（式中、Ｒ^３はＣ_１〜Ｃ_３炭化水素基である）
を有する。 In one embodiment, the amine is a tertiary amine. In a preferred embodiment, the amine has the following general structure:

(Wherein R ³ is a C ₁ -C ₃ hydrocarbon group)
Have

を有する、Ｎ−メチルジシクロヘキシルアミン（Ｃ_１３Ｈ_２５Ｎ、Ｍ_ｗ＝１９５ｇ／モル）である。この実施態様では、アミンは、ＡＳＴＭ Ｄ２８９６に従って試験した際に、約２８１ｍｇ ＫＯＨ／ｇのＴＢＮを有する。 By way of example, in one embodiment, the amine has the following structure:

N-methyldicyclohexylamine (C ₁₃ H ₂₅ N, M _w = 195 g / mol). In this embodiment, the amine has a TBN of about 281 mg KOH / g when tested according to ASTM D2896.

を有する、Ｎ−シクロヘキシル−Ｎ−エチルシクロヘキサンアミン（Ｃ_１４Ｈ_２７Ｎ、Ｍ_ｗ ２０９ｇ／モル）である。この実施態様では、アミンは、ＡＳＴＭ Ｄ２８９６に従って試験した際に、約２６８ｍｇ ＫＯＨ／ｇのＴＢＮを有する。 As another example, in one embodiment, the amine has the following structure:

N-cyclohexyl-N-ethylcyclohexaneamine (C ₁₄ H ₂₇ N, M _w 209 g / mol). In this embodiment, the amine has a TBN of about 268 mg KOH / g when tested according to ASTM D2896.

を有する、ジイソプロピルエチルアミン（Ｃ_８Ｈ_１９Ｎ、Ｍ_ｗ１２９ｇ／モル）である。この実施態様では、アミンは、ＡＳＴＭ Ｄ２８９６に従って試験した際に、約４２８ｍｇ ＫＯＨ／ｇのＴＢＮを有する。このように、構造（ＶＩ）のアミンは、より低いＴＢＮを有するアミンよりも少ない量で潤滑剤組成物に添加することができ、潤滑剤組成物の望ましいＴＢＮ値を達成する。即ち、この構造及び塩基性のために、アミン構造（ＶＩ）は非常に有効であり、潤滑剤組成物への優れた溶解性を有する。 As yet another example, in a preferred embodiment, the amine has the following structure:

Diisopropylethylamine (C ₈ H ₁₉ N, M _w 129 g / mol). In this embodiment, the amine has a TBN of about 428 mg KOH / g when tested according to ASTM D2896. Thus, the amine of structure (VI) can be added to the lubricant composition in lesser amounts than amines with lower TBN, achieving the desired TBN value of the lubricant composition. That is, because of this structure and basicity, the amine structure (VI) is very effective and has excellent solubility in the lubricant composition.

を有するＮ，Ｎ−ジメチルシクロヘキサンアミン（Ｃ_８Ｈ_１７Ｎ、Ｍ_ｗ１２７ｇ／モル）である。この実施態様では、アミンはＡＳＴＭ Ｄ２８９６に従って試験した際に、約４２７ｍｇ ＫＯＨ／ｇのＴＢＮを有する。このように、構造（ＶＩＩ）のアミンは、より低いＴＢＮを有するアミンよりも少量で潤滑剤組成物に添加することができ、潤滑剤組成物の望ましいＴＢＮ値を達成し、また潤滑剤組成物に溶解性である。 In one embodiment, the amine has the following structure:

N, N-dimethylcyclohexaneamine (C ₈ H ₁₇ N, M _w 127 g / mol). In this embodiment, the amine has a TBN of about 427 mg KOH / g when tested according to ASTM D2896. Thus, the amine of structure (VII) can be added to the lubricant composition in a smaller amount than an amine having a lower TBN to achieve the desired TBN value of the lubricant composition, and the lubricant composition It is soluble in

Various other non-limiting examples of amines have the following structure:

及びそれらの組み合わせから選択されるアミンを含む。 As noted above, the lubricant composition can include a combination of different amines. For this purpose, any combination of the different structures of the above amines can be included in the lubricant composition. For example, in various embodiments, the lubricant composition is:

And amines selected from combinations thereof.

  In various embodiments, the amine is about 1 to 45%, alternatively about 2 to about 40%, alternatively about 2 to about 15%, alternatively about 2 to about 15%, based on the total weight of the lubricant composition. It is present in the lubricant composition in an amount of 12 wt%, alternatively about 5 to about 12 wt%, alternatively about 2 to about 10 wt%, alternatively about 6 to about 10 wt%. Alternatively, the amine is greater than about 2%, alternatively greater than about 3%, alternatively greater than about 4%, or greater than about 5% by weight, based on the total weight of the lubricant composition. Or greater than about 6 wt.%, Alternatively greater than about 7 wt.%, Alternatively greater than about 8 wt.%, Alternatively greater than about 9 wt.%, Or greater than about 10 wt.%. It can be included in things. The amount of amine can vary outside the above ranges, but is typically both integer and decimal values within these ranges. Further, it should be understood that more than one amine may be included in the lubricant composition, in which case the total amount of all amines included is within the above range.

  The lubricant composition also includes a detergent. The detergent is typically selected from overbased or neutral sulfonic acid metal salts, phenol metal salts and salicylic acid metal salts, and combinations thereof. For example, in various embodiments, the detergent is selected from sulfonic acid metal salts, phenol metal salts, salicylic acid metal salts, carboxylic acid metal salts, thiophosphonic acid metal salts, and combinations thereof. In one embodiment, the detergent comprises an overbased metal sulfonate, such as calcium sulfonate. In another embodiment, the detergent comprises an overbased metal salicylate, such as a calcium metal salicylate. In yet another embodiment, the detergent comprises an alkylphenol salt detergent.

  Detergents typically include metals such as sodium, potassium, calcium, etc. that can react to form ash. It is believed that the inclusion of amine in the additive composition reduces the amount of detergent required in the lubricant composition. Since the amine is ashless and there is a reduction in excess amounts of detergent, such as overbased detergents that form ash and plate out on cylinder walls and other engine components, Harmful effects are also reduced.

  When included, the detergent is present in the lubricant composition from about 0.1 to about 35 weight percent, alternatively from about 0.1 to about 30 weight percent, alternatively from about 0, based on the total weight of the lubricant composition. 0.1 to about 25%, alternatively about 0.1 to about 20%, alternatively about 0.1 to about 15%, alternatively about 0.1 to about 10%, alternatively about 0.1 to about 5% % May be included. Alternatively, the detergent is less than about 35%, less than about 30%, less than about 25%, less than about 20%, less than about 15%, less than about 10%, respectively, based on the total weight of the lubricant composition. It can be included in the lubricant composition in an amount of less than about 5%, less than about 5%, or less than about 1% by weight. The amount of detergent can vary outside the above ranges, but is typically both an integer value and a decimal value within these ranges. In addition, it should be understood that more than one detergent may be included in the lubricant composition, in which case the total amount of all detergents included is within the above range.

  The lubricant composition may also include a dispersant. In various embodiments, the lubricant composition does not include a dispersant. The lubricant composition is free or substantially free of dispersant (eg, less than about 5%, alternatively less than about 2%, alternatively about 1%, based on the total weight of the lubricant composition). %, Or less than about 0.1% by weight, or about 0% by weight), the compatibility and solubility of the amine in the lubricant composition may include a reduced amount of dispersant in the lubricant composition. Or it may be possible to exclude it.

  In another embodiment, the lubricant composition includes a dispersant. The dispersant comprises a polyalkenyl succinic anhydride polyamine and / or a polyalkenyl succinimide polyamine. While not intending to be bound by theory, dispersants (eg, polyalkenyl succinic anhydride polyamines and / or polyalkenyl succinimide polyamines), if present, contribute to the solubility of the amine in the base oil. I think that. Additional dispersants, such as polybutenylphosphonic acid derivatives and basic magnesium, calcium and barium sulfonates and phenolates, succinic acid esters and alkylphenolamines (Mannich bases), polyalkeneamine dispersants, and combinations thereof are also lubricated It can be added to the agent composition.

In one embodiment, the dispersant comprises a polyalkenyl succinic anhydride polyamine, such as polybutenyl succinic anhydride polyamine ("PIBSA-PAM"). In this embodiment, the PIBSA-PAM is about 200 to about 3000 g / mol, alternatively about 200 to about 1500 g / mol, alternatively about 400 to about 1200 g / mol, alternatively about 600 to about 1200 g / mol, alternatively about 850 to about 850. It has a weight average molecular weight (M _w ) of 950 g / mol, or about 900 g / mol.

In another embodiment, the dispersant comprises a polyalkenyl succinimide polyamine, such as polyisobutylene succinimide ("PIBSI"). In this embodiment, the PIBSI has a mass of about 200 to about 3000 g / mol, alternatively about 200 to about 1500 g / mol, alternatively about 600 to about 1200 g / mol, alternatively about 850 to about 950 g / mol, alternatively about 900 g / mol. It has an average molecular weight (M _w ).

  When included, the dispersant is about 0.1 to about 15%, alternatively about 0.1 to about 10%, alternatively about 0.1 to about 8% by weight, based on the total weight of the lubricant composition. Or about 0.1 to about 6%, alternatively about 0.1 to about 4%, alternatively about 0.1 to about 3%, alternatively about 1 to about 3% by weight in the lubricant composition. Can be included. Alternatively, the dispersant is an amount of less than about 15%, less than about 12%, less than about 10%, less than about 5%, or less than about 4% by weight, each based on the total weight of the lubricant composition. In the lubricant composition. The amount of dispersant may vary outside the above ranges, but is typically both an integer value and a decimal value within these ranges. Furthermore, it should be understood that more than one dispersant may be included in the lubricant composition, in which case the total amount of all dispersants included is within the above range.

  The lubricant composition may also include a base oil. Base oils are classified according to the American Petroleum Institute (API) base oil compatibility guidelines. That is, the base oil may be further described as one or more of five base oils: Group I (sulfur content greater than 0.03% by weight, saturates less than 90% by weight, viscosity index 80-120); Group II (sulfur content 0.03% by mass or less, and saturates with 90% by mass or more, viscosity index 80 to 120); Group III (sulfur content 0.03% by mass or less, and saturates with 90% by mass or more) , Viscosity index 120 or higher); group IV (all of polyalphaolefins (PAO)); and group V (group I, group II, group III, or anything else not included in group IV).

  In one embodiment, the base oil is an American Petroleum Institute (API) Group I oil, an API Group II oil, an API Group III oil, an API Group IV oil, an API Group V oil, and Selected from those combinations. In another embodiment, the base oil comprises an API Group I oil. In yet another embodiment, the base oil comprises an API Group II oil.

In yet another embodiment, a base oil may be defined as a synthetic oil that further comprises one or more alkylene oxide polymers and interpolymers, and derivatives thereof. The terminal hydroxyl group of the alkylene oxide polymer can be modified by esterification, etherification, or similar reactions. These synthetic oils can be prepared by forming a polyoxyalkylene polymer through polymerization of ethylene oxide or propylene oxide, which further react to form a synthetic oil. For example, alkyl and aryl ethers of these polyoxyalkylene polymers can be used. For example, methyl polyisopropylene glycol ether having an average molecular weight of 1000; diphenyl ether of polyethylene glycol having a molecular weight of 500 to 1000, or diethyl ether of polypropylene glycol having a molecular weight of 1000 to 1500 and / or their mono- and polycarboxylic acids esters, for example, the acetic acid esters, mixed C ₃ -C ₈ fatty acid esters, and C ₁₃ oxo acid diester of tetraethylene glycol may also be utilized as a base oil.

  The base oil may be from about 40 to about 99.9% by weight, alternatively from about 50 to about 99.9% by weight, alternatively from about 50 to about 95% by weight, alternatively from about 50 to about 95%, based on the total weight of the lubricant composition. It can be included in the lubricant composition in an amount of 80% by weight. Alternatively, the base oil may be greater than about 50 wt%, alternatively greater than about 60 wt%, alternatively greater than about 70 wt%, alternatively greater than about 75 wt%, or greater than about 50 wt%, based on the total weight of the lubricant composition It can be included in the lubricant composition in an amount greater than 80 wt%, alternatively greater than about 85 wt%, alternatively greater than about 90 wt%, alternatively greater than about 95 wt%. The amount of base oil can vary outside the above ranges, but is typically both integer and decimal values within these ranges. Furthermore, it should be understood that two or more base oils may be included in the lubricant composition, in which case the total amount of all base oils included is within the above range.

  The lubricant composition may also include an antiwear additive. Any antiwear additive known in the art can be included. Suitable non-limiting examples of antiwear additives include zinc dialkyldithiophosphate ("ZDDP"), zinc dialkyldithiophosphate, sulfur and / or phosphorus and / or halogen containing compounds such as sulfurized olefins and vegetable oils, dialkyls Zinc dithiophosphate, alkylated triphenyl phosphate, tolyl phosphate, tricresyl phosphate, chlorinated paraffin, alkyl and aryl di- and trisulfides, amine salt of mono- and dialkyl phosphate, amine salt of methylphosphonic acid, diethanolaminomethyl Tolyltriazole, bis (2-ethylhexyl) aminomethyltolyltriazole, 2,5-dimercapto-1,3,4-thiadiazole derivative, ethyl 3-[(diisopropoxyphosphinothioyl) thio] Lopionate, triphenylthiophosphate (triphenylphosphorothioate), tris (alkylphenyl) phosphorothioate and mixtures thereof (eg, tris (isononylphenyl) phosphorothioate), diphenylmonononylphenyl phosphorothioate, isobutylphenyldiphenyl phosphorothioate, 3-hydroxy-1 , 3-thiaphosphetane 3-oxide dodecylamine salt, trithiophosphate 5,5,5-tris [isooctyl 2-acetate], derivatives of 2-mercaptobenzothiazole, for example 1- [N, N-bis (2-ethylhexyl) Ashless antiwear additives such as aminomethyl] -2-mercapto-1H-1,3-benzothiazole, ethoxycarbonyl-5-octyldithiocarbamate, phosphorus, and / Or combinations thereof. In one embodiment, the antiwear additive comprises ZDDP.

  When included, the antiwear additive is from about 0.1 to about 10 weight percent, alternatively from about 0.1 to about 5 weight percent, alternatively from about 0.1 to about 4 weight percent, based on the total weight of the lubricant composition. % By weight, alternatively about 0.1 to about 3% by weight, alternatively about 0.1 to about 2% by weight, alternatively about 0.1 to about 1% by weight, alternatively about 0.1 to about 0.5% by weight Can be included in the lubricant composition. Alternatively, the antiwear additive is less than about 10%, less than about 9%, less than about 8%, less than about 7%, less than about 6% by weight, each based on the total weight of the lubricant composition. The lubricant composition may be included in an amount of less than about 5%, less than about 4%, less than about 3%, less than about 2%, or less than about 1% by weight. The amount of antiwear additive can vary outside the above ranges, but is typically both an integer value and a decimal value within these ranges. In addition, it should be understood that more than one antiwear additive may be included in the lubricant composition, in which case the total amount of antiwear additive included is within the above range.

  The lubricant composition may also include a pour point depressant. Any pour point depressant known in the art can be included. Pour point depressants are typically selected from polymethacrylates and alkylated naphthalene derivatives, and combinations thereof.

  When included, the pour point depressant is from about 0.01 to about 5%, alternatively from about 0.01 to about 2%, alternatively from about 0.01 to about 1 based on the total weight of the lubricant composition. The lubricant composition may be included in an amount of mass%, alternatively about 0.01 to about 0.5 mass%. Alternatively, the pour point depressant is in an amount of less than about 5%, less than about 4%, less than about 3%, less than about 2%, and about 1% by weight, respectively, based on the total weight of the lubricant composition. Can be included in the lubricant composition. The amount of pour point depressant can vary outside the above ranges, but is typically both an integer value and a decimal value within these ranges. Furthermore, it should be understood that more than one pour point depressant may be included in the lubricant composition, in which case the total amount of all pour point depressants included is within the above range. .

  The lubricant composition can also include an antifoaming agent. Any antifoaming agent known in the art can be included. The antifoaming agent is typically selected from silicone-based antifoaming agents, acrylate copolymer antifoaming agents, and combinations thereof.

  When included, the antifoaming agent can be included in the lubricant composition in an amount of about 1 ppm to about 1000 ppm, alternatively about 1 ppm to about 500 ppm, alternatively about 1 ppm to about 400 ppm, based on the total weight of the lubricant composition. . Alternatively, the antifoaming agent may be included in the lubricant composition in amounts of less than about 1000 ppm, less than about 500 ppm, and less than about 400 ppm, each based on the total weight of the lubricant composition. The amount of antifoam can vary outside the above ranges, but is typically both integer and decimal values within these ranges. Furthermore, it should be understood that two or more antifoaming agents may be included in the lubricant composition, in which case the total amount of all antifoaming agents included is within the above range.

  In addition to the above components, such as ashless fuel additives, base oils, detergents, etc., the lubricant composition may further include one or more additions to improve chemical and / or physical properties. Agents can be included. Non-limiting examples of one or more additives include antioxidants, metal passivation, and viscosity index improvers. Each additive may be used alone or in combination. When included, one or more additives may be included in various amounts.

  In various embodiments, the lubricant composition comprises or consists essentially of an amine, an API Group I oil, a detergent comprising a metal sulfonate, and a dispersant comprising a polybutenyl succinic anhydride polyamine. Or consist of them.

  In some embodiments, the lubricant is substantially free of detergent. The term “substantially free” as used immediately above and throughout the present disclosure is less than about 5% by weight, alternatively less than about 4% by weight, alternatively about 4% by weight, based on the total weight of the lubricant composition. It means an amount of detergent (or other additive) of less than 3%, alternatively less than about 2%, alternatively less than about 1%, alternatively less than about 0.01%, alternatively about 0% by weight.

  In various embodiments, the lubricant composition may be further described as a fully formulated lubricant or as an engine oil. In one embodiment, the term “fully formulated lubricant” means the entire final composition that is the final commercial oil. This final commercial oil can contain, for example, antiwear additives, dispersants, detergents, and other conventional additives.

（式中、Ｒ^４は直鎖状Ｃ_９〜Ｃ_１１炭化水素基である）
を有するアミン、
（ｉｉ）スルホン酸金属塩を含む清浄剤、及び
（ｉｉｉ）ポリブテニル無水コハク酸ポリアミン
を含むか、それらからなるか、又は本質的にそれらからなる。 In various preferred embodiments, the lubricant composition comprises
(I) The following structure:

(Wherein R ⁴ is a linear C _{9 to} C ₁₁ hydrocarbon group)
An amine having
(Ii) a detergent comprising a sulfonic acid metal salt, and (iii) a polybutenyl succinic anhydride polyamine comprising, consisting of, or consisting essentially of them.

（式中、Ｒ^３はＣ_１〜Ｃ_３炭化水素基である）
を有する無灰燃料添加剤としてのアミン、
（ｉｉ）スルホン酸金属塩を含む清浄剤、及び
（ｉｉｉ）ポリブテニル無水コハク酸ポリアミン
を含むか、それらからなるか、又は本質的にそれらからなる。 In another preferred embodiment, the lubricant composition is
(I) The following structure:

(Wherein R ³ is a C ₁ -C ₃ hydrocarbon group)
An amine as an ashless fuel additive having
(Ii) a detergent comprising a sulfonic acid metal salt, and (iii) a polybutenyl succinic anhydride polyamine comprising, consisting of, or consisting essentially of them.

を有する無灰燃料添加剤としてのアミン、
（ｉｉ）スルホン酸金属塩を含む清浄剤、及び
（ｉｉｉ）ポリブテニル無水コハク酸ポリアミン
を含むか、それらからなるか、又は本質的にそれらからなる。 In yet another preferred embodiment, the lubricant composition is
(I) The following structure:

An amine as an ashless fuel additive having
(Ii) a detergent comprising a sulfonic acid metal salt, and (iii) a polybutenyl succinic anhydride polyamine comprising, consisting of, or consisting essentially of them.

  As suggested above, amines exhibit excellent solubility in lubricant compositions. Without being bound by theory, as explained above, the combination of branched and cyclic groups on the amine is believed to contribute to the solubility of the amine. In addition, the amine TBN allows the use of a minimum amount of amine in the lubricant composition and also reduces the amount of detergent in the lubricant composition. Furthermore, various structural embodiments of the above amines in combination with detergents including metal salts of sulfonic acids and polybutenyl succinic anhydride polyamines can be used at various temperatures (eg, −4 ° C., 4 ° C., 45 ° C. or Resulting in a uniform lubricant composition that does not phase separate and / or produce precipitates (with excellent solubility) even when stored at 60 ° C. for various times (eg, 90 days) Conceivable. For example, in various embodiments, the lubricant composition is exposed for 90 days at a temperature of 60 ° C., 90 days at a temperature of 45 ° C., 90 days at a temperature of 4 ° C. and / or 90 days at a temperature of −4 ° C. If done, it remains uniform and does not phase separate. In the meantime, the lubricant composition is ashless (or low ash). The term “ashless” as used herein to describe a lubricant composition refers to an amine-containing lubricant composition that is ashless and thus can contribute to the formation of ash. Means a lubricant composition containing less.

  The lubricant composition may also be further defined as ashless or ash containing, as per ASTM D 874 or as known in the art. Typically, the term “ashless” means the absence of significant amounts of metals such as sodium, potassium, calcium, and the like. Of course, the use of the term ashless is intended to reflect the use of amines that are ashless, and the subsequent reduction in detergents that may contribute to ash in the composition, Thus, it should be understood that the lubricant composition is not particularly limited to the definition of being ashless, since the lubricant composition can be interpreted as an ash-containing, for example, a “reduced ash composition”. It is.

  In one or more embodiments, the lubricant composition is 8% or less, 7% or less, 6% or less, 5% or less by weight based on the total weight of the lubricant composition when tested according to ASTM D874. Hereinafter, it can be classified as a low SAPS lubricant having a sulfated ash content of 4% by mass or less, 3% by mass or less, 2% by mass or less, 1% by mass or less, or 0.5% by mass or less. The term “SAPS” means sulfated ash, phosphorous and sulfur. Alternatively, in one or more embodiments, the lubricant composition is less than about 45,000 ppm, alternatively less than about 40,000 ppm, alternatively less than about 35,000 ppm, alternatively less than about 30,000 ppm, when tested according to ASTM D874. Or alternatively as having a sulfated ash content of less than about 25,000 ppm.

  The present disclosure also provides a method for lubricating an internal combustion engine. An internal combustion engine lubrication method includes the steps of injecting fuel and a lubricant composition into a cylinder to form a mixture, and combusting the mixture via compression ignition. In various embodiments, the fuel and lubricant composition is injected into the cylinder at a ratio of about 100: 1 to about 1000: 1, alternatively about 200: 1 to about 400: 1. Lubricant compositions and their components, such as amines, detergents, etc. are shown and described above. In one embodiment, the fuel comprises sulfur, for example diesel fuel containing sulfur.

  In a typical embodiment, the lubricant composition is used in a diesel engine (also known in the art as a compression ignition engine). A diesel engine is typically an internal combustion engine that uses compression heat to initiate ignition and burn fuel, and a lubricant composition is injected into a cylinder / combustion chamber. Compression ignition engines are in contrast to spark ignition engines, such as gasoline engines or gas engines (which use gaseous fuel as opposed to gasoline), which use spark plugs to ignite an air fuel mixture. In one particular embodiment, the combustion engine is further defined as a marine compression ignition internal combustion engine, ie a marine combustion engine. In another special embodiment, the combustion engine is further defined as a compression ignition internal combustion engine for trains, i.e. a train or railway combustion engine. Of course, ashless fuel additives are not limited to use in combustion engines for marine applications. The use of ashless fuel additives in other combustion engines in other applications, such as automobiles, trucks, aircraft, trains, motorcycles, scooters, ATVs, lawn equipment, etc. is also contemplated herein. .

  In this method, a mixture comprising a synthetic fuel and a lubricant composition is injected / introduced into a cylinder of the internal combustion engine, burned to move the piston, and move the internal combustion engine. In one embodiment, the fuel and lubricant are combined prior to injection into the cylinder. In another embodiment, fuel and lubricant are injected separately into the cylinder. In yet another embodiment, fuel and lubricant are combined in a cylinder.

  The following examples are intended to illustrate the present disclosure and should in no way be considered as limiting the scope of the present disclosure.

Examples Examples 1-3 are lubricant compositions according to the present disclosure. Examples 1-3 include amines, detergents, and dispersants. The ingredients in the lubricant compositions of Examples 1-3 and the amounts of each ingredient are listed in Table 1 below.

To form Examples 1-3, a base composition (base concentrate) is first formed. To form the base composition, base oil, detergent, antifoam, pour point depressant, and dispersant are added to the container and blended at 70 ° C. for 1 hour. Next, antiwear additives and antioxidants are added to the container and the ingredients are further blended at 50 ° C. for 1 hour to form the base composition. Once formed, the base composition, amine, and additional base oil are blended in the amounts listed in Table 1 for an additional hour at 50 ° C. to form each example.

Base concentrate ingredients:
The detergent is an overbased calcium sulfonate detergent.
The antifoaming agent is a silicone antifoaming agent.
The pour point depressant is a polymethacrylate pour point depressant.
The dispersant is a polyisobutylene polysuccinic anhydride polyamine.
The antioxidant is an amine.
The antiwear additive is ZDDP.

（式中、Ｒ^４は直鎖状Ｃ_９〜Ｃ_１１炭化水素基である）
を有するアミンである。 Amine A has the following structure:

(Wherein R ⁴ is a linear C _{9 to} C ₁₁ hydrocarbon group)
Is an amine.

  Amine B is N, N-dimethylcyclohexaneamine.

  Amine C is diisopropylethylamine.

  Base oil A is a high viscosity base oil.

  Base oil B is a low viscosity base oil.

Various physical properties of the lubricant compositions of Examples 1 to 3 are listed in Table 2 below.

  Referring to Table 2, Examples 1-3 containing amines produce low concentrations of sulfated ash. Furthermore, Examples 1-3 show excellent solubility, do not phase separate and / or produce precipitates upon storage.

  The accompanying claims are not limited to the expressions and specific compounds, compositions, or methods described in the detailed description, and these vary between the specific embodiments falling within the scope of the appended claims. It should be understood that this is possible. Different, special, and / or unexpected results are independent of all other Markush members for any Markush group that relies on this specification to illustrate specific features or aspects of the various embodiments It should be understood that it is obtained from each member of the respective Markush group. Each member of the Markush group may be relied upon individually and / or in combination to provide adequate support for specific embodiments within the scope of the appended claims.

  Also, any ranges and subranges that are relied upon in describing the various embodiments of this invention are included, independently and comprehensively, within the scope of the appended claims, and such values are expressly set forth herein. It should be understood that all ranges, including integer values and / or decimal values therein, are described and considered, even if not done. Those skilled in the art will appreciate that the listed ranges and subranges fully describe and enable various embodiments of the invention, and that such ranges and subranges are related to one half, one third, four minutes. It will be readily understood that it can be described in more detail in 1/5, etc. By way of example only, the “0.1-0.9” range is the lower third, ie 0.1-0.3, the middle third, ie 0.4-0.6. Can be described in more detail in the upper third, i.e. 0.7-0.9, which are included individually and comprehensively within the scope of the appended claims, individually and And / or is comprehensively dependent and provides appropriate support for certain embodiments within the scope of the appended claims.

  In addition, for terms that define or modify ranges such as “at least”, “greater than”, “less than”, “below”, etc., it is understood that such terms include subranges and / or upper or lower limits It should be. As another example, a range of “at least 10” essentially includes at least 10-35 subranges, at least 10-25 subranges, 25-35 subranges, etc., each subrange being individually And / or comprehensively, providing appropriate support for specific embodiments within the scope of the appended claims. Finally, individual numerical values within the disclosed ranges may depend on particular embodiments within the scope of the appended claims, and provide appropriate support for the embodiments. For example, the range “from 1 to 9” includes various individual integers, such as 3, and individual numbers including a decimal point (or fraction), such as 4.1, which are specified within the scope of the appended claims. Depending on the embodiment, and provides appropriate support for the embodiment.

  It should be understood that the present invention has been described in an illustrative manner and that the terminology used is intended to be in the scope of terms of description rather than limitation. Many modifications and variations of the present invention are possible in light of the above teachings, and the invention may be practiced otherwise than as specifically described.

Claims (12)

A lubricant composition for a compression ignition internal combustion engine,
(I) an amine as an ashless fuel additive, at least one of the following general structures:

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a C _{1 to} C ₁₅ hydrocarbon group, and at least one of R ¹ , R ² and R ³ is branched) Or a cyclic hydrocarbon group) or

(Wherein R ⁴ is a linear or cyclic C _{3 to} C ₁₁ hydrocarbon group)
Have, when tested in accordance with ASTM D2896, having a total base number of 200-600 mg KOH / g and (TBN), the amine; and (ii) sulfonic acid metal salts, phenol metal salts, salicylic acid metal salts, carboxylic acid A detergent selected from metal salts, metal salts of thiophosphonic acids, and combinations thereof;
Including
The TBN of the lubricant composition is 20 to 130 mg KOH / g when tested according to ASTM D2896; and the TBN contribution of the amine to the TBN of the lubricant composition is greater than 30%;
The lubricant composition.   The lubricant composition of claim 1, wherein the TBN contribution of the amine to the TBN of the lubricant composition is greater than the TBN contribution of the detergent to the TBN of the lubricant composition.   The lubricant composition of claim 1 or 2, wherein the amine has a TBN of 250 to 550 mg KOH / g when tested according to ASTM D2896. R ^{1, R 2,} and at least two of ^{R 3} is a branched or cyclic _C 2 -C ₇ hydrocarbon group, a lubricant composition according to claim 1. The amine has the following general structure:

(Wherein R ³ is a C ₁ -C ₃ hydrocarbon group)
The lubricant composition according to claim 1 , comprising: The lubricant composition according to any one of claims 1 to 5 , wherein the detergent comprises an overbased metal. Further comprising polyisobutylene succinic anhydride polyamine and / or polyalkenyl succinimide polyamine having a weight average molecular weight ( _Mw ) of 200 to 3000 g / mol and / or an American Petroleum Institute (API) Group I oil, API 7. The base oil of any one of claims 1 to 6 , further comprising a base oil selected from Group II oils, API Group III oils, API Group IV oils, API Group V oils, and combinations thereof. The lubricant composition according to item. Lubricant composition according to any one of claims 1 to 7 , which remains homogeneous and does not phase separate when exposed to a temperature of 60 ° C for 90 days. 9. A lubricant composition according to any one of claims 1 to 8 having a sulfated ash value of less than 45,000 ppm when tested according to ASTM D874. A lubricant composition for a compression ignition internal combustion engine,
(I) The following structure:

An amine as an ashless fuel additive having
The lubricant composition comprising (ii) a detergent containing a metal salt of sulfonic acid, and (iii) a polybutenyl succinic anhydride polyamine. A marine cylinder lubricant composition comprising:
(I) an amine as an ashless fuel additive, at least one of the following general structures:

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a C _{1 to} C ₁₅ hydrocarbon group, and at least one of R ¹ , R ² and R ³ is branched) Or a cyclic hydrocarbon group) or

(Wherein R ⁴ is a linear or cyclic C _{3 to} C ₁₁ hydrocarbon group)
Have, when tested in accordance with ASTM D2896, having a total base number of 200-600 mg KOH / g and (TBN), and the amine,
(Ii) comprising a detergent selected from sulfonic acid metal salts, phenol metal salts, salicylic acid metal salts, carboxylic acid metal salts, thiophosphonic acid metal salts, and combinations thereof ;
The TBN of the lubricant composition is 20 to 130 mg KOH / g when tested according to ASTM D2896, and the TBN contribution of the amine to the TBN of the lubricant composition is greater than 30%;
The marine cylinder lubricant composition. A method for lubricating an internal combustion engine using the lubricant composition according to any one of claims 1 to 11 ,
(A) A step of injecting a fuel and a lubricant composition into a cylinder to form a mixture, wherein the lubricant composition comprises:
(I) an amine as an ashless fuel additive, at least one of the following general structures:

(Wherein R ¹ , R ² and R ³ are each independently a hydrogen atom or a C _{1 to} C ₁₅ hydrocarbon group, and at least one of R ¹ , R ² and R ³ is branched) Or a cyclic hydrocarbon group) or

(Wherein R ⁴ is a linear or cyclic C _{3 to} C ₁₁ hydrocarbon group)
Have, when tested in accordance with ASTM D2896, having a total base number of 200-600 mg KOH / g and (TBN), and the amine,
(Ii) comprising a detergent selected from sulfonic acid metal salts, phenol metal salts, salicylic acid metal salts, and combinations thereof;
The TBN of the lubricant composition is 20 to 130 mg KOH / g when tested according to ASTM D2896, and the TBN contribution of the amine to the TBN of the lubricant composition is the lubricant composition More than 30% of said TBN of said step; and (B) combusting the mixture comprising fuel and lubricant composition by compression ignition;
Said method.